Novel bis tetraphenylmethanes



3,530,152 NOVEL BIS TETRAPHENYLMETHANES Emery G. Tokoli, Princeton,N.J., assignor to Minnesota Mining and Manufacturing Company, St. Paul,Minn., a corporation of Delaware No Drawing. Filed July 27, 1966, Ser.No. 568,111 Int. Cl. C09b 11/10 US. Cl. 260-390 9 Claims ABSTRACT OF THEDISCLOSURE Compounds of the formula This invention relates to thepreparation of certain high molecular weight aromatic compounds. Moreparticularly the invention relates to the preparation of di andpolyfunctional bis tetraarylmethanes.

It is an object of the invention to provide certain high molecularweight aromatic compounds which are useful as chemical intermediates.

It is another object of the invention to provide intermediates in thepreparation of surfactants.

It is another object of this invention to provide certain di, tri andtetra functional compounds that can be used to prepare useful highlyaromatic polymers.

It is another object of the invention to provide high molecular weightreactive compounds.

Other objects of the invention will be apparent from the disclosureshereinafter made.

In accordance with the above and other objects of the invention, it hasbeen found that polyfunctional bis tetraarylmethanes which are valuableintermeditaes for the preparation of various polymers can be prepared.

These bis tetraarylmethane derivatives have the structural formula:

T nited States Patent 0 wherein Ar, Ar, Ar, D, Q and Y as previouslydefined, X is chlorine or bromine and (H) is a replaceable aromatichydrogen atom.

The first step in this process, i.e. the preparation of compounds oftype III, is carried out in a solution using a suitable inert solvent,such as carbon disulfide or tetra chloroethylene, at a temperatureranging from about 40 to 150 C. in the presence of a condensationcatalyst. Effective catalysts for this reaction are anhydrous Lewisacids (also known as Friedel-Crafts catalysts) such as aluminumchloride, aluminum bromide, ferric chloride, antimony pentachloride,molybdenum pentachloride, indium trichloride, gallium trichloride, etc.

The first halogen atom is removed from compound I quite easily in itsreaction with II to form III. Once III is formed, however, the reactionstops since compounds of this type are quite stable. When the preferredcatalyst, aluminum chloride, is used, a stable complex is formed betweenthe product (compound III) and the aluminum chloride. This complex canbe decomposed with water and the desired product isolated.

In the final step of the process, the remaining halogen (X) is removed,utilizing the more reactive compound IV. The step is carried in either amelt or a solution and ordinarily at a temperature ranging from to 200C. A catalyst is generally not needed although a condensation catalyst(such as those listed above) is desirable in some cases. An inertsolvent, such as tetrachloroethylene, or an organic carboxylic acid,such as acetic acid or propionic acid, can also be utilized.

Among the specific intermediate compounds useful in preparing thecompounds of the invention are the following:

anidiamine,

o-amino phenol, o-phenylene The compounds of the invention are useful aschemical intermediates. They can, for example, be reacted through the Qgroups with compounds capable of reacting therewith and containing longchain alkyl groups to form surfactants. Thus a long chain isocyanate,such as octadecyl isocyanate, can be reacted with compounds of theinvention to form surfactants.

The compounds of the invention are also useful intermediates in thepreparation of polymers. Those in which one or both Y groups are otherthan hydrogen are trior tetrafunctional and in some cases will formheteroaromatic polymers such as benzimidazoles (where Y and Q are bothamino and are ortho oriented) or benzoxazoles (Where Y is amino and Q ishydroxy and they are ortho oriented). When both Y and Q are hydroxy,

branched and crosslinked polymers can be obtained. The dihydroxy bistetraphenylmethanes can be reacted with diacidchlorides to formpolyesters and with phosgene to prepare polycarbonates and the diaminobis tetraphenylmethanes can be reacted with dicarboxylic anhydrides to 4cooled and allowed to stand for 2 hours. The material is then filtered;the filter cake is washed with hexane and dried to give 357 g. (62.7%)of a white product, M.P. 173175 C.

In a second preparation of the same compound, a

form polyimides. Compounds of the invention having still white productmelting at 175177 C. is obtained. other Y and Q groups (e.g. mercaptans)are monomers Analytical results on this material are as follows: foradditional types of polymers. calcjd 39 29 2 (p 0 H, C1,

Among the diacid chlorides useful as cornonomers with 12.9. Found(percent): C. 80.2; H, 5.1; Cl, 12.3. the diols of the invention to formpolyester are terephthaloyl chloride, isophthaloyl chloride, phthaloylExample 2 chloride, naphthalene 2,6-diacidchloride and napthalene Thepreparation of d h l i h l- 1,8-diacidchloride. Among the dianhydridessuitable for methanekthgn reaction with the diamines of the invention toform first gis-(tritylchloride)ether 1 4 0.0 l d the respectivepolyamide acids and then, after additional phanol (2&2 g 03 mole) ammixed in a fl k and heated heating at high temperature, the polyimidesare those on an Oil bath f 4 hours at 1 1 0 h fl k i listed in US Pat.3,179,634 at 6011mm lines 35 and cooled and the contents are removed andslurried in follOWihgglacial acetic acid. The mixture is filtered; andthe white The Polymers P p from the Compounds of the filter cake iswashed with acetic acid, and methanol; and vention are generallythermally and oxidatively stable dried in vacuum to give 12 grams (87%)of product, (assuming that suitable coreactants are selected) and 5 27can be linear or crosslinked, as desired. They find uses in A l i c l df C H O (percent); C, 87 43; many areas, e.g. in shaped objects, ascoating materials H, 558, F und (percent): C, 86.0; H, 5.64. for varioussubstrates, as filaments, unsupported films, Thi bi h l, d i it high ltii t, i etc. readily soluble in dioxane.

Having described the invention in broad terms it is now morespecifically illustrated by examples showing the best EXAMPLE 3 modepresently contemplated of practicing the invention.

In these examples, where not otherwise indicated, parts The Preparanonof bls(p'ammophenyltnphenylmeth' of solids are by weight and of liquidsby volume and temans) ether peratures are in degrees centigrade A 100ml. flask fitted-with a magnetlc stirrer, thermometer, and a condenser,is charged with bis-(trltylchlorlde) THE COMPOUNDS OF THE INVENTIONether (11.4 gr., 0.02 mole), aniline hydrochloride (13.0

Example 1 g., 0.1 mole), and 50 ml. of acetic acid. The resulting thickslurry is heated to reflux and maintained at this The preparation ofbis-(trityl chloride) ether. temperature until the theoretical quantityof HCl is The S-liter flask fitted with a stirrer, thermometer, evolved.The material is filtered; the filter cake is washed and a condenser ischarged with benzophenone dichloride free of mother liquor with aceticacid; and dried to give (471.4 g. 1.97 mole), diphenyl ether (169.0 g.,0.99 11.9 g., (79%) of a purple product, M.P. 244-250". mole), and 2liters of tetrachloroethylene. The solution 40 The amine hydrochlorideis converted to the free amine is cooled to 10 and AlCl (268.0 g., 1.97mole) is added by suspending the salt in aqueous methanol and treatingat such a rate that the temperature does not exceed 17. with methanolicsodium hydroxide. The white amine is The cooling bath is removed and themixture is slowly filtered and dried, M.P. 301304. This diamine, despitewarmed to reflux and maintained at this temperature units high meltingpoint, is readily soluble in tetrahydrofuran til the evolution of gasceases. and dioxane.

The mixture is then cooled to 25 and divided into Analysis.Calculated:NE. 343. Found: NE. 351. five portions. Each portion is mixed with 80ml. of water In a similar manner, the additional compounds shown andbeaten in a blender until a white color appears. The below are prepared(the reactants and products of the inmaterial is then filtered and theorganic filtrates are comvention being designated by Roman numerals ashereinbined. Hexane (400 ml.) is added and the solution is before).

Example Number I II IV V 4 01 (I) C1 0 I 3 31 (I31 2 W 5 Cl-(J-Cl @S@Same a ab ve H2N@ S TABLE COntinHEd Example Number I II IV V I 6 o I l-2 lTII-Iz I-I 1| I I 10 Same as above Same as above @N 2 2 *Meltingpoint 223-225 C.

POLYMERS PREPARED FROM THE COMPOUNDS 70 OF THE INVENTION Example 14Preparation of a polyimide from his (p-arninophenyltriphenylrnethane)ether and pyromellitic dianhydride.

Bis-(p-aminophenyltriphenylmethane) ether (3.505 g., 0.01 equivalent) isweighed into a container under N Dry dirnethylacetamide (44.2 ml.) isadded and the solution is cooled. While a N atmosphere is maintainedpyromellitic dianhydride (1.091 g., 0.01 equivalent) is added 75 withvigorous stirring. The inherent viscosity of the result- 7 ing solutionis 0.36 (measured as a 1% solution of polymer in dimethylacetamide).

The material is imidized with heat and a film is cast that is soluble inCHCI and CH CI Similarly useful polyimides can be prepared from theother diamines of the invention.

Example Preparation of a polycarbonate frombis-(p-hydroxyphenyltriphenylmethane) ether and phosgene.

A 100 ml. four-neck flask fitted with a thermometer, stirrer, condenserand a bubbler for the introduction of phosgene is dried and flushed withnitrogen for 15 minutes. Bis-(p-hydroxyphenyltriphenylmethane) ether(4.3 g., 0.0063 mole) and 50 cc. of pyridine are placed in the flask andthe mixture is heated to 90 to dissolve the diphenol. The solution iscooled to phosgene is then added with gentle stirring. The temperatureis maintained at 25-30 by means of an ice-water bath, applied asnecessary.

When a yellow color develops, the phosgene addition is stopped and alittle bisphenol-pyridine solution is added. The mixture is stirreduntil practically all the color is discharged. The polymer is isolatedby pouring the mixture into four times its volume of water with vigorousstirring. The precipitate is filtered; washed with water; and suspendedin 500 ml. of water at 80 for 15 minutes. The polymer is filtered;washed with water; and dried in vac uum at 90 to yield 4.7 g. of thewhite polycarbonate. The infrared spectrum of this material confirms itsidentity as the polycarbonate.

Similarly, useful polycarbonates can be prepared from the otherdialcohols of the invention.

Example 16 Preparation of a polyester frombis-(p-hydroxyphenyltriphenylmethane) ether and terphthaloyl chloride.

A 50 ml. flask fitted with a N flush, stirrer, and a condenser ischarged, in a N filled glove box, withbis-(phydroxyphenyltriphenylmethane) ether 5.088 g., 0.015 eq.)terphthaloylchloride (1.523 g., 0.015 eq.) and ml. of a chlorinated highboiling aromatic solvent. While a N atmosphere is maintained the mixtureis heated. When the temperature reaches 224 the gas begins to evolve anda light brown solution results. The solution 8 is heated to 300-330 andmaintained at this temperature for 1 hour, then cooled and poured into500 ml. of heptane, whereupon a white fibrous material appears. Thismaterial is isolated by filtration, washed with heptane, and dried togive 6.1 g. of a white product; '=0.55 (measured as a 0.5% solution ofpolymer in chloroform). Its infrared spectrum indicates that it is apolyester. It is found to be soluble in CH Cl CHCl chlorobenzene, etc. Along term heat aging study shows a 10% weight loss in hours at 600 F. inair, and 680 hours at 500 F.

What is claimed is: 1. A compound having the formula Y Ar Ar Q-ArJAI"DAr( Ar Y wherein each Ar is phenyl or halophenyl, each Ar' isphenyl having no substituents other than Y and Q, each Ar" isunsubstituted phenylene, D is -O', S, NH or -CH each Y is NH OH, SH orH, and each Q is NH OH or SH.

2. A compound according to claim 1 wherein each Ar is phenyl.

3. A compound according to claim 1 wherein Q is hydroxyl and Y ishydrogen.

4. A compound according to claim 2 wherein Q is hydroxyl and Y ishydrogen.

5. A compound according to claim 1 wherein Q is amino and Y is hydrogen.

6. A compound according to claim 2 wherein Q is amino and Y is hydrogen.

7. Bis (p-hydroxyphenyltriphenylmethane) ether.

8. Bis (p-aminophenyltriphenylmethane) ether.

9. Bis (p-aminophenyltriphenylmethane) thioether.

References Cited UNITED STATES PATENTS 3,196,159 7/1965 Laszlo 260-390LORRAINE A. WEINBERGER, Primary Examiner L. A. THAXTON, AssistantExaminer U.S. Cl.-X.R.

